US8067522B2 - Low viscosity, alkoxysilane-functional prepolymers and a process for their preparation - Google Patents
Low viscosity, alkoxysilane-functional prepolymers and a process for their preparation Download PDFInfo
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- US8067522B2 US8067522B2 US11/512,487 US51248706A US8067522B2 US 8067522 B2 US8067522 B2 US 8067522B2 US 51248706 A US51248706 A US 51248706A US 8067522 B2 US8067522 B2 US 8067522B2
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- 0 C[Si](C)([Y])*N=C=O Chemical compound C[Si](C)([Y])*N=C=O 0.000 description 5
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/71—Monoisocyanates or monoisothiocyanates
- C08G18/718—Monoisocyanates or monoisothiocyanates containing silicon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4825—Polyethers containing two hydroxy groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2190/00—Compositions for sealing or packing joints
Definitions
- the present invention relates to low viscosity, alkoxysilane-functional prepolymers, to a process for preparing them and to adhesives, sealants, primers or coatings prepared from these prepolymers.
- Alkoxysilane-functional polyurethanes which crosslink via silane polycondensation are well established.
- a review article on this topic is found for example in “Adhesives Age” 4/1995, page 30 ff. (authors: Ta-Min Feng, B. A. Waldmann).
- Alkoxysilane-terminated, moisture-curing, one-component polyurethanes are increasingly being used as elastomeric coating, sealing and adhesive compositions in construction and in the automotive industry.
- alkoxysilane-functional polyurethanes can be prepared in accordance with U.S. Pat. No. 3,627,722 or U.S. Pat. No. 3,632,557 by reacting, for example, polyether polyols with an excess of polyisocyanate to form an NCO-containing prepolymer which is then further reacted with an amino-functional alkoxysilane.
- the resulting alkoxysilane-functional prepolymer contains a high concentration of urea groups and urethane groups, which results in products having high viscosities.
- One effective way of reducing at least the portion of the hydrogen bond density resulting from the urea groups is to use secondary aminosilanes to generate substituted ureas.
- a variety of methods have been proposed for this purpose: U.S. Pat. No. 3,627,722 and U.S. Pat. No. 3,632,557 use alkyl-substituted aminosilanes; U.S. Pat. No. 4,067,844 uses an addition reaction of acrylates with the primary aminosilane; EP-A 596 360 uses an addition reaction of maleic esters with the primary aminosilane; and EP-A 676 403 introduces aryl-substituted aminosilanes. All of these methods, however, are able to replace only one hydrogen atom on the terminal urea group; all other urea protons and urethane protons continue to contribute, via hydrogen bonds, to a high viscosity.
- binders In the case of a stoichiometric reaction of isocyanate-functional alkoxysilane units, binders are obtained which, due to inadequate capping, especially when using very long chain polyethers, are unable to crosslink sufficiently on curing. This leads to very soft polymers having a high surface tack and a deficient resilience, or a high plastic deformability.
- prepolymers having the required properties can be prepared by initially reacting long-chain polyethers or OH-functional polyether prepolymers with an excess of isocyanate functional alkoxysilane and removing the excess of isocyanate groups by subsequent allophanatization or reaction with a low molecular weight NCO-reactive compound.
- the present invention relates to a process for preparing alkoxysilane-functional prepolymers by reacting
- the present invention also relates to the alkoxysilane-functional prepolymers obtained by the process of the invention.
- X, Y, and Z may independently of one another also be bridging.
- X, Y and Z in formula I) independently of one another are methoxy or ethoxy.
- R is preferably a linear, branched or cyclic alkylene radical having 1 to 8 carbon atoms, more preferably a methylene or propylene radical.
- component A) has a number average molecular weight of 3000 g/mol to 20,000 g/mol, more preferably of 8000 g/mol to 18,000 g/mol.
- Polyoxyalkylene polyols useful as polyol component A) in accordance with the invention are the polyethers known from polyurethane chemistry and include the adducts or coadducts of tetrahydrofuran, styrene oxide, ethylene oxide, propylene oxide, butylene oxides or epichlorohydrin, particularly ethylene oxide and/or propylene oxide, that are prepared using dihydric to hexahydric starter molecules such as water or the polyols described below for use as component C) or amines having 1- to 4-NH bonds.
- propylene oxide polyethers which have an average of 2 to 4 hydroxyl groups and can contain up to 50% by weight of incorporated polyethylene oxide units.
- the polyethers may be prepared by catalysis with potassium hydroxide, for example, and also polyethers prepared by the more recent processes based on double metal cyanide catalysts.
- the latter polyethers generally have a particularly low level of terminal unsaturation of less than 0.07 meq/g, contain a significantly lower proportion of monols and generally have a low polydispersity of less than 1.5.
- Preferred polyethers are those prepared by double metal cyanide catalysis, more preferably those which have a polydispersity of 1.0 to 1.5, most preferably 1.0 to 1.3.
- the polydispersity can be determined in known manner using gel permeation chromatography (GPC) to determine not only the number average molecular weight (M n ) but also the weight average molecular weight (M w ).
- GPC gel permeation chromatography
- M n number average molecular weight
- M w weight average molecular weight
- the polydispersity, PD, is given by M w /M n .
- polyethers examples include the Acclaim® 4200, Acclaim® 6300, Acclaim® 8200, Acclaim® 12200 and Acclaim® 18200 products (or the corresponding Acclaim® xx00N grades) from Bayer MaterialScience AG, Leverkusen, Del. These polyoxyalkylene polyols can be used in pure form or as a mixture of different polyethers. It is possible, although less preferred, to admix polyols having lower molecular weights.
- the polyethers preferably have average OH functionalities of 1.8 to 4. In polyether mixtures it is possible to use polyethers having OH functionalities of 1 to 6.
- OH-functional prepolymers obtained by reacting polyoxyalkylene polyols having number average molecular weights of 1000 g/mol to 15,000 g/mol with diisocyanates to form OH-functional prepolymers having a molecular weight of preferably 3000 g/mol to 20,000 g/mol, more preferably 8000 to 18,000 g/mol, as described, for example, in U.S. Pat. No. 4,345,053 or EP-A 931 800.
- the use of such OH functional prepolymers is not preferred.
- Suitable compounds containing isocyanate and alkoxysilane groups B) include alkoxysilane-functional monoisocyanates having a molecular weight of 140 g/mol to 500 g/mol. Examples include isocyanatomethyltrimethoxysilane, isocyanatomethyl-triethoxysilane, (isocyanatomethyl)methyldimethoxysilane, (isocyanatomethyl)methyl-diethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropylmethyl-dimethoxysilane, 3-isocyanatopropyltriethoxysilane and 3-isocyanatopropylmethyl-diethoxysilane. 3-isocyanatopropyltrimethoxysilane is preferred.
- isocyanate-functional silanes prepared by reacting a diisocyanate with an aminosilane or thiosilane, e.g. as described in U.S. Pat. No. 4,146,585 or EP-A 1136495. However, the use of these compounds is not preferred.
- the process of the invention is carried out in two stages.
- an allophanatization is used as a second step, it is also possible to carry out that allophanatization step together with the urethanization of components A) and B) in the first step.
- the urethanization of components A) and B) can optionally be carried out with a catalyst.
- Suitable catalysts for curing include organotin compounds and amine catalysts.
- organotin compounds include dibutyltin diacetate, dibutyltin dilaurate, dibutyltin bisacetoacetonate and tin carboxylates such as tin octoate.
- tin catalysts can be used optionally in combination with amine catalysts such as aminosilanes or 1,4-diazabicyclo[2.2.2]octane.
- dibutyltin dilaurate is used as urethanization catalyst.
- the catalyst component where used, is employed in amounts of 0.001 to 5.0% by weight, preferably 0.001% to 0.1% by weight and more preferably 0.005% to 0.05% by weight, based on the solids content of the product.
- the urethanization of components A) and B) is carried out at temperatures of 20 to 200° C., preferably 40 to 120° C. and more preferably of 60 to 100° C.
- the reaction is continued until complete conversion of the OH groups of the compounds of component A) is achieved.
- the progress of the reaction can be monitored by means of suitable instruments installed in the reaction vessel and/or by means of analyses on samples taken. Appropriate methods are known. Examples include viscosity measurements, measurements of NCO content, measurements of refractive index, measurements of OH content, gas chromatography (GC), nuclear magnetic resonance (NMR) spectroscopy, infrared (IR) spectroscopy and near-infrared (NIR) spectroscopy.
- the first option is to add another NCO-reactive component C), which in a subsequent reaction step is reacted with the remaining NCO groups.
- Suitable compounds for this purpose are low molecular weight compounds having a number average molecular weight of up to 400 g/mol and containing one or more alcohol, amine or thiol groups. These compounds may contain other reactive groups. Thiol compounds are less preferred, due to their odor, which is frequently unpleasant.
- Examples of monofunctional alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomeric pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol, n-hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols, hydroxymethyl-cyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol; diethylene glycol monoalkyl ethers such as diethylene glycol monobutyl ether; unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleyl alcohol; aromatic alcohols
- polyfunctional alcohols include ethylene glycol, triethylene glycol, tetraethylene glycol, propane-1,2 and -1,3-diol, butane-1,4 and -1,3-diol, hexane-1,6-diol, octane-1,8-diol, neopentyl glycol, 1,4-bis(hydroxymethyl)cyclohexane, bis(hydroxymethyl)tricyclo[5.2.1.0 2,6 ]decane or 1,4-bis(2-hydroxyethoxy)benzene, 2-methyl-1,3-propanediol, 2,2,4-trimethylpentanediol, 2-ethyl-1,3-hexanediol, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, 1,4-phenoldimethanol, bisphenol A, tetrabromobisphenol A, glycerol, trimethylo
- Amines which can be employed include not only primary but also secondary amines, such as ethylamine, propylamine, isopropylamine, n-butylamine, sec-butylamine, tert-butylamine, hexylamine, 2-ethylhexylamine, cyclohexylamine, benzylamine, dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, bis-(2-ethylhexyl)amine, N-methyl- and N-ethylcyclohexylamine or dicyclohexylamine and also heterocyclic secondary amines such as morpholine, pyrrolidine, piperidine or 1H-pyrazole. Also suitable are aromatic amines, such as aniline, diphenylamine or appropriately substituted derivatives.
- compounds containing isocyanate-reactive groups and silane groups include aminopropyltrimethoxysilane, mercaptopropyltrimethoxysilane, aminopropylmethyldimethoxysilane, mercaptopropylmethyl-dimethoxysilane, aminopropyltriethoxysilane, mercaptopropyltriethoxysilane, aminopropyl-methyldiethoxysilane, mercaptopropylmethyldiethoxysilane, aminomethyltrimethoxysilane, aminomethyltriethoxysilane, (aminomethyl)methyldimethoxysilane, (aminomethyl)methyl-diethoxysilane, N-butylaminopropyltrimethoxysilane, N-ethylaminopropyltrimethoxysilane, N-phenylaminopropyltrimethoxysilane, N-(3-trie
- component C) that is at least equivalent to the remaining NCO content. It is preferred to have 1 to 1.5 equivalents of C) per equivalent of the NCO groups remaining after the urethanization of A) and B).
- the removal of the excess isocyanate content with component C) is carried out at temperatures of 20 to 200° C., preferably 40 to 120° C. and more preferably of 60 to 100° C.
- component C) has a low volatility a correspondingly low temperature is selected.
- the reaction is continued until complete removal of the NCO groups (free NCO group content ⁇ 0.5% by weight, preferably ⁇ 0.1% by weight, and more preferably ⁇ 0.05% by weight) has been achieved. This can be checked analytically by the methods previously described.
- the second option for removing the NCO groups present in the reaction product of components A) and B) is an allophanatization reaction. In this case no further component C) is added and the remaining NCO groups are reacted with the urethane groups formed from components A) and B).
- Suitable allophanatization catalysts include zinc salts, such as zinc octoate, zinc acetylacetonate and zinc 2-ethylcaproate; or tetraalkylammonium compounds, such as N,N,N-trimethyl-N-2-hydroxy propylammonium hydroxide, N,N,N-trimethyl-N-2-hydroxy propylammonium 2-ethylhexanoate or choline 2-ethylhexanoate.
- zinc octoate zinc 2-ethylhexanoate
- the tetraalkylammonium compounds more preferably zinc octoate.
- the catalyst is used in amounts of 0.001% to 5.0% by weight, preferably 0.01% to 1.0% by weight and more preferably 0.05% to 0.5% by weight, based on the solids content of the product of the process.
- the allophanatizing catalyst can be added in one portion, in several portions or continuously. It is preferred to add the whole amount in one portion.
- the allophanatization reaction is carried out at temperatures of 20 to 200° C., preferably 40 to 160° C., more preferably 60 to 140° C., and most preferably 80 to 120° C.
- the process of the invention may be carried out continuously in a static mixer, extruder or compounder, for example, or batchwise in a stirred reactor, for example.
- the process of the invention is preferably carried out in a stirred reactor.
- the progress of the reaction can be monitored as described above by means of suitable instruments installed in the reaction vessel and/or by means of analyses on samples taken.
- the allophanatization reaction is preferably continued until the NCO content of the product is below 0.05% by weight, more preferably below 0.03% by weight.
- the compounds of the invention are especially suitable for use as binders for producing isocyanate-free elastic polyurethane adhesives and sealants, preferably for automotive engineering and the construction sector. These products crosslink on exposure to atmospheric moisture via silanol polycondensation. Additionally, they are suitable for producing primers and coatings.
- Suitable basic fillers include precipitated or ground chalks, metal oxides, metal sulphates, metal silicates, metal hydroxides, metal carbonates and metal hydrogen carbonates.
- examples of other fillers include reinforcing and nonreinforcing fillers such as carbon black, precipitated silicas, pyrogenic silicas, ground quartz or diverse fibers. Both the basic fillers and also the further reinforcing or nonreinforcing fillers may optionally have undergone surface modification. Particularly preferred basic fillers are precipitated or ground chalks and also pyrogenic silicas. Mixtures of fillers can also be used.
- Suitable plasticizers include phthalic esters, adipic esters, alkylsulphonic esters of phenol, or phosphoric esters. Additionally, long-chain hydrocarbons, polyethers and vegetable oils can be used as plasticizers. Suitable thixotropic agents include pyrogenic silicas, polyamides, hydrogenated castor oil derivatives or polyvinyl chloride.
- Suitable curing catalysts include any organometallic compounds and amine catalysts known to promote silane polycondensation.
- Particularly suitable organometallic compounds include compounds of tin and of titanium.
- Examples of preferred tin compounds include dibutyltin diacetate, dibutyltin dilaurate, dioctyltin maleate and tin carboxylates such as tin(II) octoate or dibutyltin bisacetoacetonate.
- the tin catalysts may optionally be used in combination with amine catalysts such as amino silanes or 1,4-diazabicyclo[2.2.2]octanes.
- Preferred titanium compounds include alkyl titanates, such as diisobutyl bis(ethyl acetoacetate)titanate.
- preferred catalysts are those which have an especially high base strength, such as amines with an amidine structure.
- Preferred amine catalysts include 1,8-diazabicyclo[5.4.0]undec-7-ene or 1,5-diazabicyclo[4.3.0]non-5-ene.
- Suitable driers include alkoxysilyl compounds such as vinyltrimethoxysilane, methyltrimethoxysilane, i-butyltrimethoxysilane, and hexadecyltrimethoxysilane.
- Adhesion promoters include the known functional silanes such as the previously mentioned aminosilanes and also N-aminoethyl-3-aminopropyltrimethoxy and/or N-aminoethyl-3-aminopropylmethyldimethoxysilane, epoxysilanes and/or mercaptosilanes.
- the crosslinked polymers have very good tensile strength and high modulus at low elongations.
- the tackiness (tack) is very much lower than in the case of the non-inventive, comparative examples.
- tack tack
- the ambient temperature of 23° C. prevailing at the time when the experiments were conducted is designated RT.
- the reaction was cooled to 50° C. and 1.67 g of butanediol were mixed in. Stirring was continued at 50° C. for about 90 minutes until an NCO content was no longer detected.
- the resulting polyurethane prepolymer contained alkoxysilyl end groups and had a viscosity of 35,000 mPa ⁇ s (23° C.).
- the resulting polyurethane prepolymer contained alkoxysilyl end groups and had a viscosity of 49,700 mPa ⁇ s (23° C.).
- the product was filled into a polyethylene cartridge and stored at room temperature.
- the sealant composition After storage for one day the sealant composition cured with a skin-forming time of 10 to 20 minutes.
- the mechanical properties of the formulated binders compared to the comparative example, showed significantly increased values for the Shore A hardness, the tensile strength and the 100% modulus and also a reduced (subjective) tack of the polymer surfaces.
- the improvements are a result of the significantly improved crosslinking of the long polymer chains, which is achieved with the compounds according to the invention.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyurethanes Or Polyureas (AREA)
- Sealing Material Composition (AREA)
- Silicon Polymers (AREA)
- Paints Or Removers (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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DE102005041953A DE102005041953A1 (de) | 2005-09-03 | 2005-09-03 | Niedrigviskose alkoxysilangruppenaufweisende Prepolymere, ein Verfahren zu ihrer Herstellung sowie ihre Verwendung |
DE102005041953.4 | 2005-09-03 | ||
DE102005041953 | 2005-09-03 |
Publications (2)
Publication Number | Publication Date |
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US20070055035A1 US20070055035A1 (en) | 2007-03-08 |
US8067522B2 true US8067522B2 (en) | 2011-11-29 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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US11/512,487 Active 2026-12-06 US8067522B2 (en) | 2005-09-03 | 2006-08-30 | Low viscosity, alkoxysilane-functional prepolymers and a process for their preparation |
Country Status (16)
Country | Link |
---|---|
US (1) | US8067522B2 (no) |
EP (1) | EP1924621B1 (no) |
JP (1) | JP5909316B2 (no) |
CN (1) | CN101253209B (no) |
AT (1) | ATE419291T1 (no) |
AU (1) | AU2006286874B2 (no) |
BR (1) | BRPI0616128A2 (no) |
CA (1) | CA2620991C (no) |
DE (2) | DE102005041953A1 (no) |
DK (1) | DK1924621T3 (no) |
ES (1) | ES2318789T3 (no) |
HK (1) | HK1123818A1 (no) |
NO (1) | NO20081437L (no) |
PL (1) | PL1924621T3 (no) |
TW (1) | TWI405782B (no) |
WO (1) | WO2007025668A1 (no) |
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US20120245241A1 (en) * | 2009-12-09 | 2012-09-27 | Bayer Intellectual Property Gmbh | Polyurethane prepolymers |
US10093765B2 (en) | 2016-06-27 | 2018-10-09 | Evonik Degussa Gmbh | Alkoxysilane-functionalized allophanates |
US10093826B2 (en) | 2016-06-27 | 2018-10-09 | Evonik Degussa Gmbh | Alkoxysilane-functionalized allophanate-containing coating compositions |
US10336856B2 (en) * | 2016-06-27 | 2019-07-02 | Evonik Degussa Gmbh | Alkoxysilane- and allophanate-functionalized coating materials |
US10336854B2 (en) | 2016-06-27 | 2019-07-02 | Evonik Degussa Gmbh | Alkoxysilane-functionalized and allophanate-functionalized urethanes |
US10730961B2 (en) | 2015-07-29 | 2020-08-04 | Bridgestone Corporation | Processes for preparing functionahzed polymers, related functionalizing compound and preparation thereof |
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US7732554B2 (en) * | 2006-09-21 | 2010-06-08 | Momentive Performance Materials Inc. | Process for preparing a curable silylated polyurethane resin |
EP2014314A1 (de) | 2007-07-10 | 2009-01-14 | Bayer Innovation GmbH | Verfahren zur Herstellung von Polyurethan-Schäumen für die Wundbehandlung |
DE102007032342A1 (de) * | 2007-07-11 | 2009-01-15 | Bayer Materialscience Ag | Verfahren zur Herstellung von Polyurethan-Schäumen auf Basis von speziellen alkoxysilanfunktionellen Polymeren |
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DE102007058483A1 (de) | 2007-12-04 | 2009-06-10 | Henkel Ag & Co. Kgaa | Härtbare Zusammensetzungen enthaltend silylierte Polyurethane |
DE102008003743A1 (de) * | 2008-01-10 | 2009-07-16 | Henkel Ag & Co. Kgaa | Härtbare Zusammensetzungen enthaltend weichelastische silylierte Polyurethane |
EP2199351A1 (de) | 2008-12-19 | 2010-06-23 | Sika Technology AG | Flüssigfolie auf Basis von silanterminierten Polymeren |
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2006
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- 2006-08-23 CA CA2620991A patent/CA2620991C/en not_active Expired - Fee Related
- 2006-08-23 BR BRPI0616128-6A patent/BRPI0616128A2/pt not_active IP Right Cessation
- 2006-08-23 WO PCT/EP2006/008275 patent/WO2007025668A1/de active Application Filing
- 2006-08-23 AT AT06791626T patent/ATE419291T1/de active
- 2006-08-23 ES ES06791626T patent/ES2318789T3/es active Active
- 2006-08-23 JP JP2008528387A patent/JP5909316B2/ja not_active Expired - Fee Related
- 2006-08-23 DE DE502006002528T patent/DE502006002528D1/de active Active
- 2006-08-23 CN CN2006800321684A patent/CN101253209B/zh active Active
- 2006-08-23 AU AU2006286874A patent/AU2006286874B2/en not_active Ceased
- 2006-08-23 EP EP06791626A patent/EP1924621B1/de active Active
- 2006-08-23 DK DK06791626T patent/DK1924621T3/da active
- 2006-08-30 US US11/512,487 patent/US8067522B2/en active Active
- 2006-09-01 TW TW095132267A patent/TWI405782B/zh not_active IP Right Cessation
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2008
- 2008-03-19 NO NO20081437A patent/NO20081437L/no not_active Application Discontinuation
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
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US20120245241A1 (en) * | 2009-12-09 | 2012-09-27 | Bayer Intellectual Property Gmbh | Polyurethane prepolymers |
US10730961B2 (en) | 2015-07-29 | 2020-08-04 | Bridgestone Corporation | Processes for preparing functionahzed polymers, related functionalizing compound and preparation thereof |
US10093765B2 (en) | 2016-06-27 | 2018-10-09 | Evonik Degussa Gmbh | Alkoxysilane-functionalized allophanates |
US10093826B2 (en) | 2016-06-27 | 2018-10-09 | Evonik Degussa Gmbh | Alkoxysilane-functionalized allophanate-containing coating compositions |
US10336856B2 (en) * | 2016-06-27 | 2019-07-02 | Evonik Degussa Gmbh | Alkoxysilane- and allophanate-functionalized coating materials |
US10336854B2 (en) | 2016-06-27 | 2019-07-02 | Evonik Degussa Gmbh | Alkoxysilane-functionalized and allophanate-functionalized urethanes |
Also Published As
Publication number | Publication date |
---|---|
TW200722447A (en) | 2007-06-16 |
EP1924621B1 (de) | 2008-12-31 |
WO2007025668A1 (de) | 2007-03-08 |
JP5909316B2 (ja) | 2016-04-26 |
NO20081437L (no) | 2008-04-02 |
AU2006286874B2 (en) | 2011-06-02 |
TWI405782B (zh) | 2013-08-21 |
DK1924621T3 (da) | 2009-04-14 |
DE102005041953A1 (de) | 2007-03-08 |
CN101253209B (zh) | 2012-04-04 |
HK1123818A1 (en) | 2009-06-26 |
AU2006286874A1 (en) | 2007-03-08 |
DE502006002528D1 (de) | 2009-02-12 |
ATE419291T1 (de) | 2009-01-15 |
ES2318789T3 (es) | 2009-05-01 |
CA2620991C (en) | 2014-05-27 |
US20070055035A1 (en) | 2007-03-08 |
EP1924621A1 (de) | 2008-05-28 |
PL1924621T3 (pl) | 2009-06-30 |
BRPI0616128A2 (pt) | 2011-12-27 |
CN101253209A (zh) | 2008-08-27 |
JP2009507088A (ja) | 2009-02-19 |
CA2620991A1 (en) | 2007-03-08 |
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